Microbicidal compositions

ABSTRACT

There are described the use of α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol as a microbicide for the protection of industrial materials, and compositions containing this compound.

[0001] The invention relates to the use of the compoundα-(4-chlorophenyl-α-(1-cyclopropyl-ethyl)-1H-1,2,4-triazole-1-ethanol(cyproconazole) as a microbicide for the protection of industrialmaterials, and to synergistic mixtures containing this compound.

[0002] It has been disclosed that the azole derivatives described inDE-OS (German Published Specification) 3,406,993 can be used forprotecting plants.

[0003] The present invention relates to the use of an azole derivativeof the formula (I)

[0004] its metal salts or acid addition compounds as a microbicide forthe protection of industrial materials.

[0005] The azole derivate can not only be in the form of the free basebut also in the form of a metal salt complex or an acid addition salt.Suitable metal salts are preferably salts of metals of main groups II toIV and subgroups I and II as well as IV to VII of the periodic table,the following being mentioned by way of example: copper, zinc,manganese, magnesium, tin, iron, calcium, aluminium, lead, chromium,cobalt and nickel.

[0006] Suitable anions of the salts are those which are derived,preferably, from the following acids: hydrohalic acids such as, forexample, hydrochloric acid and hydrobromic acid, furthermore phosphoricacid, nitric acid and sulphuric acid.

[0007] The metal salt complexes of the azole derivative can be obtainedin a simple manner by customary processes, for example by dissolving themetal salt in alcohol, for example ethanol, and adding the solution tothe azole fungicide. Metal salt complexes can be isolated in a knownmanner, for example by filtration, and, if appropriate, purified byrecrystallisation.

[0008] The following acids are preferably suitable for preparing acidaddition salts of the azole derivative: the hydrohalic acids, such as,for example, hydrochloric acid and hydrobromic acid, in particularhydrochloric acid, furthermore phosphoric acid, nitric acid, sulphuricacid, mono- and bifunctional carboxylic acids and hydroxycarboxylicacids such as, for example, acetic acid, propionic acid, 2-ethylhexanoicacid, butyric acid, mandelic acid, oxalic acid, succinic acid,2-hydroxy-ethane-dicarboxylic acid, maleic acid, fumaric acid, tartaricacid, citric acid, salicylic acid, sorbic acid, lactic acid, as well assulphonic acids, such as, for example, p-toluenesulphonic acid, p-decylphenyl sulphonic acid, p-dodecyl phenyl sulphonic acid,1,4-naphthalenedisulphonic acid, alkanesulphonic acids, benzoic acid andoptionally substituted benzoic acids.

[0009] The acid addition salts of the compounds can be obtained in asimple manner by customary salt formation methods, for example bydissolving a compound in a suitable inert solvent and adding the acid,for example, hydrochloric acid, and they can be isolated in a knownmanner, for example by filtration, and, if appropriate, purified bywashing with an inert organic solvent.

[0010] The compound (R*,R*)-α-(4-chlorophenyl-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol(cyproconazole) is particularly preferred.

[0011] Surprisingly, these compounds display a particularly powerfulmicrobicidal, in particular fungicidal, activity against microorganismswhich are relevant in the protection of materials, combined with a broadspectrum of action; they are active, above all, against moulds andwood-discolouring and wood-destroying fungi. The following groups ofmicroorganisms may be mentioned by way of example, but without imposingany limitation:

[0012] A: Wood-discolouring fungi:

[0013] A1: Ascomycetes;

[0014] Ceratocystis such as Ceratocystis minor

[0015] A2: Deuteromycetes;

[0016] Aspergillus such as Aspergillus niger

[0017] Aureobasidium such as Aureobasidium pullulans

[0018] Dactylium such as Dactylium fusarioides

[0019] Penicillium such as Penicillium brevicaule or Penicilliumvariabile

[0020] Sclerophoma such as Sclerophoma pithyophila

[0021] Scopularia such as Scopularia phycomyces

[0022] Trichoderma such as Trichoderma viride or Trichoderma lignorum

[0023] A3: Zygomycetes:

[0024] Mucor such as Mucor spinorus

[0025] B: Wood-destroying fungi:

[0026] B1: Ascomycetes:

[0027] Chaetomium such as Chaetomium globosum or Chaetomiumalba-arenulum

[0028] Humicola such as Humicola grisea

[0029] Petriella such as Petriella setifera

[0030] Trichurus such as Trichurus spiralis

[0031] B2: Basidiomycetes

[0032] Coniophora such as Coniophora puteana

[0033] Coriolus such as Coriolus versicolor

[0034] Donkioporia such as Donkioporia expansa

[0035] Glenospora such as Glenospora graphii

[0036] Gloeophyllum such as Gloeophyllum abietinum or Gloeophyllumadoratum or Gl. protactum or Gloeophyllum sepiarium or Gl. trabeum

[0037] Lentinus such as Lentinus cyathiformes or Lentinus edodes orLentinus lepideus or Lentinus grinus or L. squarrolosus

[0038] Paxillus such as Paxillus panuoides

[0039] Pleurotus such as Pleurotis ostreatus

[0040] Poria such as Poria monticola or Poria placenta or Poriavaillantii or Poria vaporaria

[0041] Serpula such as Serpula himantoides or Serpula lacrymans

[0042] Stereum such as Stereum hirsutum

[0043] Tyromyces such as Tyromyces palustris

[0044] B3: Deuteromycetes

[0045] Alternaria such as Alternaria tenius

[0046] Cladosporium such as Cladosporium herbarum

[0047] The amount of active substance employed depends on the speciesand the occurance of the microorganisms, the microbial count and themedium. The optimum dosage rate for use can be determined in each caseby test series. In general, however, it suffices to employ 0.001 to 20%by weight, preferably 0.05 to 10% by weight, of the active compoundbased on the material to be protected.

[0048] The active compound can be used as such, in the form ofconcentrates or generally customary formulations such as powder,granules, solutions, suspensions, emulsions or pastes.

[0049] The abovementioned formulations can be prepared in a manner knownper se, for example by mixing the active compound with at least onesolvent or diluent, emulsifier, dispersant and/or binder or fixative,water repellant, optionally siccatives and UV stabilisers, andoptionally colourants and pigments as well as other processingauxiliaries.

[0050] Suitable solvents or diluents are organochemical solvents orsolvent mixtures and/or a polar organic solvent or solvent mixtureand/or an oily or oil-type organochemical solvent or solvent mixtureand/or water, if appropriate together with an emulsifier and/or wettingcomposition. Customary water-insoluble oily or oil-type solvents of lowvolatility which are preferably used are the particular mineraloils/mineral-oil-containing solvent mixtures or their aromaticfractions. White spirit, petroleum or alkylbenzenes, and additionallyspindle oil and monochloronaphthalene may be mentioned as beingpreferred. The boiling ranges of these solvent (mixtures) of lowvolatility cover a range of approximately 170° C. to not more than 350°C.

[0051] The above-described oily or oil-type solvents of low volatilitycan be replaced partially by more volatile organochemical solvents.

[0052] To prepare a wood preservative, some of the above describedsolvent or solvent mixture is preferably replaced by a polarorganochemical solvent or solvent mixture. Solvents which are preferablyused are those containing hydroxyl groups, ester groups, ether groups ormixtures of this functionality. Examples which may be mentioned areesters or glycol ethers. Binders are to be understood according to theinvention as being synthetic resins, binding drying oils, for examplebased on acrylic resins, vinyl resins, polyester resins, polyurethaneresins, alkyd resins, phenol resins, hydrocarbon resins or siliconeresins which can be diluted with water or are soluble, dispersible oremulsifiable in organochemical solvents. The binder used can be employedas a solution, emulsion or dispersion. Mixtures of alkyd resins anddrying vegetable oil are preferably used. Alkyd resins with an oilcontent of between 45 and 70% are particularly preferred.

[0053] All or some of the abovementioned binder can be replaced by afixative (mixture) or a plasticiser (mixture). These additives areintended to prevent volitilisation of the active compound as well ascrystallisation or precipitation. They preferably replace 0.01 to 30% ofthe binder (based on 100% of the binder used).

[0054] The plasticisers are from the chemical classes of the phthalicesters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricesters such as tributyl phosphate, adipic esters such asdi-(2-ethylhexyl) adipate, stearates such as butyl stearate and amylstearate, oleates such as butyl oleate, gylcerol ethers orhigher-molecular-weight glycol ethers, glycerol esters as well asp-toluenesulphonic esters.

[0055] Fixatives are based, from the chemical point of view, onpolyvinyl alkyl ethers such as, for example, polyvinyl methyl ether, orketones such as benzophenone or ethylenebenzophenone.

[0056] The preferred solvent or diluent is water, if appropriate in amixture with one or more of the abovementioned solvents or diluents,emulsifiers and dispersants.

[0057] Industrial materials according to the invention are non-livematerials which have been prepared for use in industry. For example,industrial materials which are intended to be protected by the activecompound from microbial change or destruction can be glues, sizes, paperand board, textiles, leather, wood, paints and plastic articles, coolinglubricants and other materials which can be infested with, or decomposedby, microorganisms. Parts of production plants, for examplecooling-water circuits, which may be impaired by the multiplication ofmicroorganisms may also be mentioned from amongst the materials to beprotected. Preferred industrial materials beyond the scope of theinvention are glues, sizes, paper and board, leather, wood, derivedtimber products, paints, cooling lubricants, aqueous hydraulic fluidsand cooling circuits.

[0058] The active compound of the formula (I), or compositions orconcentrates containing it, are preferably employed for protecting woodand derived timber products against microorganisms, for example againstwood-destroying or wood-discolouring fungi, in particular in theprotection of tropical wood.

[0059] Wood which can be protected by the active compound of the formula(I) or by mixtures containing them is to be understood as meaning, forexample, structural timber, wooden beams, railway sleepers, componentsof bridges, jetties, vehicles made of wood, boxes, pallets, containers,telegraph poles, wooden fences, wooden lagging, windows and doors madeof wood, plywood, chipboard, joinery, or wooden products which are used,quite generally, for building houses or in building joinery.

[0060] The protection of wood is particularly effective when large-scaleimpregnating treatments, for example vacuum, double vacuum or pressuretreatments, are used.

[0061] The active compound of the formula (I) is preferably mixed withat least one other antimicrobially active substance, fungicide and, inparticular, with other active compounds, to increase the spectrum ofaction or to achieve particular effects such as, for example, anadditional protection against insects. In many cases, this results insynergistic effect, that is to say, the activity of the mixture isgreater than the activity of the individual components. Particularlypreferred components for the mixtures are, for example, the followingcompounds:

[0062] Sulphenamides, such as dichlofluanid, tolylfluanid, folpet andfluorfolpet;

[0063] Benzimidazoles, such as carbedazim, benomyl, fuberidazole,thiabendazole or their salts;

[0064] Thiocyanataes such as thiocyanatomethylthiobenzothiazole ormethylene bis-thiocyanate;

[0065] Quaternary ammonium compounds such asbenzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammoniumchloride or didecyldimethylammonium chloride;

[0066] Morpholine derivatives such as tridemorph, fenpropiomorph orfalimorph;

[0067] Azoles such as triadimefon, triadimenol, bitertanol,tebuconazole, propioconazole, azaconazole, hexaconazole, prochloraz orbromuconazole, metconazole, penconazole, difenoconazole, fenbuconazole,opus, fensilazole.

[0068]2-(2-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol;

[0069] Iodine derivatives such as diiodomethyl-p-tolyl sulphone,3-iodo-2-propinyl alcohol, 4-cdhlorophenyl-3-iodopropargyl formal,3-bromo-2,3-diiodo-2-propenyl ethylcarbonate, 2,3,3-triiodoallylalcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol,3-iodo-2-propinyl-n-butyl carbamate, 3-iodo-2-propinyl n-hexylcarbamate,3-iodo-2-propinyl cyclohexylcarbamate and 3-iodo-2-propinylphenylcarbamate; O-1-(6-Iodo-3-oxo-hex-5-myl)butylcarbamate,O-1-(6-Iodo-3-oxo-hex-5-inyl)phenylcarbamate, Nepcodide VP 305.

[0070] Phenol derivatives such as derivatives such as tribromophenol,tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen,o-phenylphenol, m-phenylphenol, p-phenylphenol or2-benzyl-4-chlorophenol;

[0071] Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol or2-Brom-2-brommethyl-glutaridinitril;

[0072] Isothiazolinones such as N-methylisothiazolin-3-one,5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one or N-octyl-isothiazolin-3-one;

[0073] Benzoisothiazolinones or4-5-trismethylen-N-methylisothiazol-3-on;

[0074] Pyridines such as 1-hydroxy-2-pyridinethione (and their sodium,iron, manganese and zinc salts) ortetrachloro-4-methylsulphonylpyridine;

[0075] Metal soaps such as tin naphthenate, tin octoate, tin2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, coppernaphthenate, copper octoate, copper 2-ethylhexanoate, copper oleate,copper phosphate, copper benzoate, zinc naphthenate, zinc octoate, zinc2-ethylhexanoate, zinc oleate, zinc phosphate or zinc benzoate;

[0076] Oxides such as tributyltin oxide, Cu₂O, CuO or ZnO;

[0077] Dialkyldithiocarbamataes such as sodium and zinc salts ofdialkylthiocarbamataes, tetramethylthiuram disulphide;

[0078] Nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile;

[0079] Benzothiazoles such as 2-mercaptobenzothiazol;

[0080] Quinolines, such as 8-hydroxyquinoline, and their copper salts;

[0081] Boron compounds, such as boric acid, boric esters or borax;

[0082] Formaldehyde and formaldehyde-releasing compounds such as benzylalcohol mono(poly)-hemiformal, oxazolidines, hexahydro-S-triazines,N-methylolchloroacetamide or paraformaldehyde;

[0083] Tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclohexyldiazeniumdioxy)-tributyltin or potassium salts thereof, orbis-N-(cyclohexyldiazeniumdioxy)-copper.

[0084] The following are preferably added as insecticide:

[0085] Phosphoric esters such as azinphos-ethyl, azinphos-methyl,1-(4-chlorophenyl)-4-(O-ethyl,S-propyl)phosphoryloxypyrazole,chloropyrifos, coumaphos, demeton, demeton-S-methyl, diazinon,dichlorvos, dimethoate, ethoprophos, etrimfos, fenitrothion, fenthion,heptenophos, parathion, parathion-methyl, phosalone, phoxim,pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos,triazophos and trichlorophon;

[0086] Carbamates such as aldicarb, bendiocarb,2-(1-methylpropyl)-phenyl methylcarbamate, butocarboxim, butoxycarboxim,carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl,oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

[0087] Organosilicon compounds, preferably dimethyl(phenyl)silylmethyl3-phenoybenzyl ethers, such as dimethyl-(4-ethoxyhpenyl)silylmethyl3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl2-phenoxy-6-pyridylmethyl ethers such as, for example,dimethyl(9-ethoxy-phenyl)silylmethyl 2-phenoxy-6-pyridylmethyl ether or[(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes, such as, forexample, (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxy-phenyl-propyl]dimethylsilane.

[0088] Pyrethroids, such as allethrin, alphamethrin, bioresmethrin,byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin,cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)cyclopropanecarboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permethrin, resmethrin and tralomethrin;

[0089] Nitroimines and nitromethylenes, such as1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid).

[0090] The mixtures, concentrates and formulations according to theinvention which have been prepared in this manner are not only activeagainst the abovementioned fungi but also, if they contain aninsecticide, against insects which destroy materials. The followinginsects which destroy materials may be mentioned by way of example,without imposing any limitation:

[0091] A: Dermaptera:

[0092]Sirex juvencus

[0093]Urocerus augur

[0094]Urocerus gigas

[0095]Urucerus gigas taignus

[0096] B: Coleoptera:

[0097]Anobium punctatum

[0098]Apate monachus

[0099]Bostrychus capucins

[0100]Chlorophores pilosus

[0101]Dendrobium pertinex

[0102]Dinoderus minutus

[0103]Ernobius mollis

[0104]Heterobostrychus brunneus

[0105]Hylotrupes bajulus

[0106]Lyctus africanus

[0107]Lyctus brunneus

[0108]Lyctus linearis

[0109]Lyctus planicollis

[0110]Lyctus pubescens

[0111]Minthea rugicollis

[0112]Priobium carpini

[0113]Ptilinus pecticornis

[0114] Sinoxylon spec.

[0115]Trogoxylon aequale

[0116]Trypto dendron spec.

[0117]Xestobium rufovillosum

[0118] Xyleborus spec.

[0119] C: Isoptera:

[0120]Coptotermes formosanus

[0121]Cryptotermes brevis

[0122]Heterotermes indicola

[0123]Kalotermes flavicollis

[0124]Mastotermes darwiniensis

[0125]Reticulitermes flavipes

[0126]Reticulitermes lucifugus

[0127]Reticulitermes santonensis

[0128]Zootermopsis nevadensis

[0129] Other active compounds which are suitable are algicides,molluscicides or active compounds against sea animals which colonise,for example, ship's bottom paints.

[0130] The following are particularly preferred as components inmixtures:

[0131] dichlofluanid, tolylfluanid,

[0132] benzyldimethyldodecylammonium chloride, didecyldimethylammoniumchloride,

[0133] tebuconazole, propiconazole, azaconazole, hexaconazole,

[0134] 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butylcarbamate,

[0135] o-phenylphenol, m-phenylphenol, p-phenylphenol,3-methyl-4-chlorophenol, thiocyanatomethylthiobenzothiazole,

[0136] N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one,

[0137] benzyl alcohol mono(poly)-hemiformal, N-methylolchloroacetamide,

[0138] phoxim,

[0139] cyfluthrin, permethrin, cypermethrin, deltamethrin, imidacloprid.

[0140] The microbicidal compositions or concentrates used for theprotection of industrial materials contain the active compound of theformula (I) in a concentration from 0.01 to 95% by weight, in particular0.01 to 60% by weight, and additionally, if appropriate, 0.001 to 95% byweight of one or more other suitable fungicides, insecticides or otheractive compounds as mentioned above.

[0141] The compositions according to the invention allow in anadvantageous manner the microbicidal compositions available to date tobe replaced by more effective ones. They have good stability propertiesand, advantageously, a broad spectrum of action.

EXAMPLE 1 Inhibition Test On Giant Colonies Of Basidiomycetes

[0142] Mycelium sections were removed from colonies of Gloeophyllumtrabeum, Coniophora puteana, Poria placenta, Lentinus tigrinus, Coriolusversicolor and Stereum sanguinolentum and incubated on an agar mediumcontaining malt extract peptone at 26° C. The inhibition of hyphalgrowth on active-compound-containing media was compared with thelongitudinal growth on media without an addition of active compound andrated as percent inhibition.

[0143] At a concentration of 10 ppm, a 100% inhibition is obtained withthe compound cyproconazole.

1. Use of the compound of the formula (I)

its metal salts or acid addition compounds as a microbicide for theprotection of industrial materials.
 2. Use according to claim 1 ,characterised in that the industrial material to be protected is wood ortimber-derived products.
 3. Microbicidal compositions for the protectionof industrial materials, containing a compound of the formula (I)according to claim 1 or its metal salts or acid addition compounds. 4.Composition according to claim 3 , characterised in that it contains, asan additional component, at least one other antimicrobially activecompound, fungicide and/or other active compound for broadening thespectrum of action or for achieving specific effects.
 5. Compositionsaccording to claim 4 , characterised in that they contain at least oneinsecticide.
 6. Method of protecting industrial materials, characterisedin that the industrial materials are treated with a compound of theformula (I) according to claim 1 .